CN103250473B - Composite diode, electronic device and preparation method thereof - Google Patents

Composite diode, electronic device and preparation method thereof Download PDF

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Publication number
CN103250473B
CN103250473B CN201180058678.XA CN201180058678A CN103250473B CN 103250473 B CN103250473 B CN 103250473B CN 201180058678 A CN201180058678 A CN 201180058678A CN 103250473 B CN103250473 B CN 103250473B
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Prior art keywords
conductive foil
electronic device
linear
conductive
serosity
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CN103250473A (en
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D·戈施
蒋鸽
杨瑞
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3M Innovative Properties Co
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3M Innovative Properties Co
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/20—Organic diodes
    • H10K10/29—Diodes comprising organic-inorganic heterojunctions
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/18—Printed circuits structurally associated with non-printed electric components
    • H05K1/182—Printed circuits structurally associated with non-printed electric components associated with components mounted in the printed circuit board, e.g. insert mounted components [IMC]
    • H05K1/185—Components encapsulated in the insulating substrate of the printed circuit or incorporated in internal layers of a multilayer circuit
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/16—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10007—Types of components
    • H05K2201/10174—Diode
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B63/00—Resistance change memory devices, e.g. resistive RAM [ReRAM] devices
    • H10B63/20—Resistance change memory devices, e.g. resistive RAM [ReRAM] devices comprising selection components having two electrodes, e.g. diodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/20—Organic diodes

Abstract

The invention discloses a kind of compound diode (100), described compound diode (100) includes the first conductive foil (110), the second conductive foil (120) and is sandwiched in non-linear polymer composite (130) between the two.Described non-linear polymer composite is included in adhesive material (140) the non-linear inorganic particle (150) that maintain.The method that the invention also discloses the electronic device preparing described compound diode and include described compound diode.

Description

Composite diode, electronic device and preparation method thereof
Technical field
Present invention relates in general to diode and the electronic device comprising diode.
Background technology
Printed circuit board (PCB) (PCB) (mounted thereon have substantial amounts of discrete component) is widely used for In electronic device.Conductive trace is generally arranged on printed circuit board (PCB) and/or in printed circuit board (PCB). Conductive trace is generally through making thin copper foil patterning (generally by etching) make.Equipped with many electricity The printed circuit board (PCB) of sub-components and parts is referred to as printed circuit assembly (PCA).Printed circuit board (PCB) is usually Two-sided, and mat the electroplates in hole layer realizes the electrical connection of opposing sides.
Printed circuit board (PCB) is generally by the lamination shape of multiple insulating barriers and the most extra conductive layer Become.Conductive layer is generally made up of thin Copper Foil.The electrolyte semi-solid preparation layer of each insulation generally uses ring Epoxy layer is combined.Printed circuit board (PCB) is general coated with solder mask, and this solder mask is usually Green.Demand according to circuit design may select multiple different electrolyte to provide different exhausted Edge value.Semi-solid preparation material known to using in printed circuit board industry includes FR-2 (phenolic aldehyde Cotton paper), FR-3 (cotton paper and epoxy resin), FR-4 (glass fabric and epoxy resin), FR-5 (glass fabric and epoxy resin), FR-6 (roughened surface glass and polyester), G-10 (glass Glass fabric and epoxy resin), CEM-1 (cotton paper and epoxy resin), CEM-2 (cotton paper and Epoxy resin), CEM-3 (glass fabric and epoxy resin), CEM-4 (glass fabric and Epoxy resin) and CEM-5 (glass fabric and polyester).
The printed circuit board (PCB) of the overwhelming majority, by layers of copper being bonded on whole substrate, is sometimes It is bonded to the both sides (generating " blank printed circuit board (PCB) ") of substrate, then applying temporarily Mask after remove unwanted copper (such as, with etching method) and only leave required copper tracing wire And prepare.There are some printed circuit board (PCB)s to be mat and (or there is the thinnest layers of copper base to space base plate Plate) above add trace and make, this generally will be by the complex process of repeatedly plating step.
In recent years, reduce printed circuit board sizes trend focused on print In the space utilization of printed circuit board.Having a kind of method is that components and parts are embedded (embedding) to printing As a part for printed circuit board (PCB) lamination structure in circuit board body.Such as, 3M company sells A series of embedding (embedding) formula electric capacity, trade name 3M embedded capacitor material (3M ECM)。
But, the quantity of the components and parts of current existing embedding form is the least, so still depositing In the demand to the components and parts that can embed in printed circuit board (PCB).
Summary of the invention
In one aspect, the invention provides a kind of composite diode, comprising:
First conductive foil,
Second conductive foil,
The non-linear polymer composite wood being sandwiched between the first conductive foil and the second conductive foil The bed of material, wherein non-linear polymer composite layer and the length of the first and second conductive foils and Width is substantially coextensive, and wherein non-linear polymer composite is included in polymer The non-linear inorganic particle that maintain in adhesive material.
On the other hand, the invention provides a kind of electronic device, it includes being embedded in printing electricity Compound diode in the plate of road, wherein this composite diode include the first conductive foil,
Second conductive foil,
The non-linear polymer composite wood being sandwiched between the first conductive foil and the second conductive foil The bed of material, and wherein this non-linear polymer composite is included in polymeric adhesive material The non-linear inorganic particle that maintain.
On the other hand, the invention provides a kind of method preparing compound diode, the method Including:
Forming ground floor serosity on the first conductive member, wherein this serosity includes hardenable viscous Non-linear inorganic particle in mixture precursor；
Second conductive member is formed second layer serosity；
Engaging this ground floor serosity and second layer serosity, wherein this serosity is sandwiched in the first conduction structure Between part and the second conductive member；And
Harden this hardenable adhesive precursor at least in part.
Advantageously, the compound diode according to the present invention can be by embedding them into printing electricity Massive traditional bright dress compound diode replaced by road plate, thus allows printed circuit board (PCB) Miniaturization；Such as, the use in compact electronic device.
Compound diode according to the present invention can be used for electronic device, and wherein they can be comprised , such as, in overload protecting circuit.Advantageously, they can be embedded in printed circuit board (PCB) In, thus allow the miniaturization of circuit design.
Therefore, in yet another aspect, the invention provides a kind of electronic device, this electronic device Including the compound diode according to the present invention.
As used herein, term " is substantially coextensive " when it refers to non-relative to length and width During linear polymer composite layer, it is intended that be coextensive relative to length and width, but allow Non-linear polymer composite layer has the slight deviations less than 5 percent gross areas on the whole.
As used herein, term " non-linear " refers to the material reversible non-thread relative to change in voltage Property electric conductivity.
As used herein, term " thin slice " refer to have much larger than (such as, at least 10 times, extremely Few 20 times or even at least 50 times big) goods of the length and width of its thickness, and wrap Include, such as, panel and volume.
After considering detailed description of the invention and appended claims, will be further understood that this The feature and advantage of invention.
Accompanying drawing explanation
Fig. 1 is the schematic side elevation of the exemplary compound diode according to the present invention；
Fig. 2 is the schematic cross sectional views of the exemplary electronic device according to the present invention；
Fig. 3 is to illustrate the figure of the nonlinear current-voltage of compound diode in example 1；With
Fig. 4 is to illustrate the figure of the nonlinear current-voltage of compound diode in example 2.
Although the above-mentioned some embodiments respectively illustrating the present invention, but as described in discuss, also It is contemplated that go out other embodiment.In all cases, the disclosure is all exemplary rather than limit Property processed the present invention is shown.Should be appreciated that those skilled in the art can be designed that a large amount of its Its modification and embodiment, these modification and embodiment are also in the principle of the present invention In scope and spirit.Accompanying drawing may be not necessarily to scale.
Detailed description of the invention
Seeing Fig. 1, exemplary compound diode 100 includes the first conductive foil 110, second Conductive foil 120 and being sandwiched between the first conductive foil 110 and the second conductive foil 120 The layer 125 of non-linear polymer composite 130.Non-linear polymer composite 130 comprises The non-linear inorganic particle 150 that maintain in polymeric adhesive material 140.Non-linear polymerization The layer 125 of thing composite 130 is relative to the first conductive foil 110 and the second conductive foil 120 Length and width the most coextensive (in the same size).
Conductive foil 110,120 can be prepared by any conductive material, usually metal, but also may be used Use other material.The example of the available conductive material that can form thin slice and/or paper tinsel include copper, Nickel, gold, silver, chromium, aluminum, palladium, rustless steel and combinations thereof.In order to be conducive to multiple Closing diode to be embedded in printed circuit board (PCB), this conductive foil is advantageously relatively thin.Such as, They can have the thickness in 10 to 150 micrometer ranges, more generally 10 to 80 microns, or The most about 35 microns.
Available non-linear inorganic particle includes, such as: carborundum, the gold of doped zinc oxide impurity Belong to oxide such as Bi, Sb, Co, Mn, Ni and/or Cr (such as, Bi2O3, Cr2O3, Sb2O3, CO2O3And MnO3)；SrTiO that is semiconductive and that adulterate3(such as, doping La2O3Or Al2O3)；The SnO of doping2And TiO2(such as, the tantalum pentoxide of doping or niobium oxygen Compound)；With calcium copper titanate granule (such as, the doping calcined at about 1100 DEG C (CCT) Or undoped p matter), this calcium copper titanate granule is that on August 26th, 2010 submits to, Entitled " COMPOSITIONS HAVING NON-LINEAR CURRENT- VOLTAGE CHARACTERISTICS " (there is the combination of nonlinear current-voltage Thing) co-pending U.S. Patent application No.12/869129 in be described, this patent Disclosure is incorporated by reference herein.
Generally should select nonlinear inorganic particle so that they have at least one dimension The size of the upper gross thickness less than Nonlinear Composite layer.Such as, non-linear inorganic particle exists The size less than 100 microns can be had at least one dimension.This includes, such as, and little ball Shape granule (the least in three dimensions) and little whisker (little in a dimension).
Polymeric adhesive material comprises the steps that elastomeric material, such as, and carbamate, silicon tree Fat or EPDM；Thermoplastic polymer, such as, polyethylene or polypropylene；Binding agent such as, Such as based on vinyl-vinyl-acetate or polyurethane those；Thermoplastic elastic Body；Gel；Thermosets, such as, such as epoxy resin；Or the group of this type of material Close, including copolymer, the combination of such as polyisobutylene and amorphous polypropylene.
Non-linear inorganic particle generally includes the (example between about 25 volume % and about 65 volume % As, about 30 to 50 volume %) non-linear polymer composite, but it is used as other Amount.
Nonlinear polymer composites also can comprise the adding for these materials known to other Add agent such as, to improve their machinability and/or the adaptability to application-specific.Close Suitable additive can include processing aid, stabilizer, antioxidant and plasticizer.
The thickness of non-linear polymer composite is usually the scope of 10 to 500 microns, more logical Often the scope of 30 to 400 microns, but it is used as other thickness.
The gross thickness of the compound diode according to the present invention is usually the scope of 10 to 600 microns, But other thickness can be used.Compound diode according to the present invention can be, such as, and rigidity Or flexibility.
Compound diode according to the present invention can be prepared by any suitable method.One example The method of property includes that formation is dispersed in hardenable (such as, curable and/or coagulable) Non-linear inorganic particle in adhesive precursor and the serosity of optional organic solvent.Then can will be somebody's turn to do Serosity coats to the first conductive member, is then laminated on the second conductive member.Or, should Serosity coats discriminably to the first conductive member and the second conductive member, then should Slurry layer is bonded together and is sandwiched between the first conductive member and the second conductive member to be formed Monolayer.Which kind of no matter by method make, once laminating three layers plate structure (the first conductive member-non- Linear polymer composite the-the second conductive member) formed, adhesive precursor is the most at least in part Hardening (such as, solidification at least in part)；Such as, by solidification resinoid precursor The situation of (such as epoxy resin) or the situation by the thermoplastic binder precursor that hardens.
Compound diode according to the present invention can be used for electronic device such as mobile phone, individual number According to assistant, sensor, television set, audio frequency apparatus, radio and computer.At this kind equipment In, they can provide (voltage) surge protection.In such an application, surge protection circuit Element (being parallel to active circuit element) responds due to the non-linear current-voltage of compound diode And surge protection is provided.Such as, the threshold of Nonlinear Composite is reached when the applied voltage of circuit During value electric field, Nonlinear Composite is transformed into conduction state from state of insulation.This behavior exists It is reversible in the range of the normal working voltage of designed device.
One example of this kind of electronic device is shown in Figure 2.Referring now to Fig. 2, electronic device, 200 comprise the compound diode 100 being embedded in printed circuit board (PCB) 270.Semiconductor chip 250 It is electrically connected respectively to the first conductive electrode 110 via the first and second conduction through holes 262,264 With the second conductive electrode 120.Non-linear polymer composite 130 is sandwiched in the first conductive electrode 110 and second between conductive electrode 120.As in figure 2 it is shown, compound diode and semiconductor chip The parallel installation of circuit and be used for overload protection is provided.
The method embedding electrical equipment (such as capacitor) in the printed circuit boards is to know in the industry And can easily transformation become for embedding according to the compound diode of the present invention.
The selection embodiment of the present invention
In the first embodiment, the invention provides a kind of compound diode, this compound diode Including:
First conductive foil,
Second conductive foil,
The non-linear polymer composite wood being sandwiched between the first conductive foil and the second conductive foil The bed of material, wherein non-linear polymer composite layer and the length of the first and second conductive foils and Width is substantially coextensive, and wherein non-linear polymer composite is included in polymer The non-linear inorganic particle that maintain in adhesive material.
In a second embodiment, the invention provides according to compound two poles described in first embodiment Pipe, wherein non-linear polymer composite includes zinc oxide or the calcium copper metatitanic acid of calcining of doping Salt.
In the third embodiment, the invention provides according to answering described in first or second embodiments Closing diode, wherein non-linear polymer composite includes zinc oxide or the calcium of calcining of doping Copper titanate.
In the fourth embodiment, the invention provides according in the first to the 3rd embodiment any one Described compound diode, wherein the first conductive foil and the second conductive foil include metal forming.
In the 5th embodiment, the invention provides and include appointing according in first to fourth embodiment The electronic device of one described compound diode.
In the sixth embodiment, the invention provides a kind of electronic device, this electronic device includes Embedding the compound diode of printed circuit board (PCB), wherein this compound diode includes the first conductive thin Sheet,
Second conductive foil,
The non-linear polymer composite wood being sandwiched between the first conductive foil and the second conductive foil The bed of material, and wherein this non-linear polymer composite is included in polymeric adhesive material The non-linear inorganic particle that maintain.
In the 7th embodiment, the invention provides according to the electronics device described in sixth embodiment Part, wherein this non-linear polymer composite comprises the zinc oxide of doping or the calcium copper titanium of calcining Hydrochlorate.
In the 8th embodiment, the invention provides according to the electricity described in the 6th or the 7th embodiment Sub-device, wherein non-linear polymer composite includes the asphalt mixtures modified by epoxy resin hardened at least in part Fat.
In the 9th embodiment, the invention provides according in the 6th to the 8th embodiment any one Described electronic device, wherein the first conductive foil and the second conductive foil include metal forming.
In the tenth embodiment, the invention provides according in the 6th to the 9th embodiment any one Described electronic device, wherein printed circuit board (PCB) constitutes mobile phone, personal digital assistant, biography A part in sensor or computer.
In the 11st embodiment, the invention provides a kind of method preparing compound diode, The method includes:
Forming ground floor serosity on the first conductive member, wherein this serosity includes hardenable viscous Non-linear inorganic particle in mixture precursor；
Second conductive member is formed second layer serosity；
Engaging this ground floor serosity and second layer serosity, wherein this serosity is sandwiched in the first conduction structure Between part and the second conductive member；With
Harden this hardenable adhesive precursor at least in part.
In the 12nd embodiment, the invention provides according to the side described in the 11st embodiment Method, the most non-linear inorganic particle comprises the zinc oxide of doping or the calcium copper titanate of calcining.
In the 13rd embodiment, the invention provides according to the 11st or the 12nd embodiment institute The method stated, wherein this hardenable adhesive precursor comprises epoxy resin.
In the 14th embodiment, the invention provides according in the 11st to the 13rd embodiment Any one described method, wherein the first conduction electricity thin slice and the second conductive foil include metal Paper tinsel.
It is further illustrated by the following non-limiting examples objects and advantages of the present invention, but these Concrete material described in example and consumption thereof, and other condition and details be not construed as to this Invention carries out improper restriction.
Example
Except as otherwise noted, otherwise all parts in the remainder of example and this specification Number, percent, ratio etc. are by weight.Unless otherwise noted, the most all of solvent It is the standard reagent level available from commercial source with material and need not be further purified and make With.
Material
Copper oxide (CuO, the purity of 99%) powder is purchased from the Ah method on mountain, Ward, Massachusetts Ai Sha (Alfa Aesar, Ward Hill.MA.)
CAF refers to 4,4 '-(9H-fluorenes-9-subunit) double (2-chloroanilines), CAS No.107934-68- 9, have another name called chloroaniline Fluorenone amine hardener, available commercially from, such as, the base of Germany Lei Genshitaofu Smear limited company (Chemos GmbH of Regenstauf Germany).
Calcium carbonate (CaCO3, the purity of 99%) and powder is available commercially from AlfaAesar (Alfa Aesar).Titanium dioxide (TiO2, the purity of 99%) and powder is purchased from New Jersey Karen Phillips The J.T. Bake (J.T.Baker, Phillipsburg, NJ) in fort
Copper oxide (CuO, the purity of 99%) powder be purchased from powder be purchased from Massachusetts irrigate The AlfaAesar (Alfa Aesar, Ward Hill.MA.) on moral mountain.
The curable epoxy of EPON RESIN 1001F low-molecular-weight bisphenol-A-derivative is commercially available From the Hexion Specialty Chemical company of Columbus, Ohio (Hexion Specialty Chemicals, Columbus, OH.).
EPON HPT RESIN 1050 curable epoxy, is phenolic resin and epoxy chloropropionate The product of alkane.Hexion Specialty Chemical company (Hexion purchased from Columbus, Ohio Specialty Chemicals, Columbus, OH.).
There is the ZnO fine powder of the doping of 20 micron granularities, be purchased from ABB Azipod Oy of Switzerland (ABB Switzerland Ltd., Switzerland.)
Example 1
In order to prepare calcium copper titanate (CaCu3Ti4O12, hereinafter represent with CCT) and powder End, by stoichiometric substantial amounts of highly purified CuO (3 molar equivalent), CaCO3(1 rubs That equivalent) and TiO2(4 molar equivalent) powder steaming in the NALGENE bottle of 500mL Distilled water (150g) use the Zirconium oxide of stabilized with yttrium oxide as abrasive media (5mm glass Powder, is available from the Connecticut State Mancunian Ying Foman advanced material (Inframat Advanced Materials of Manchester, Connecticut) carry out moistening ball milling, place the bottle in wide simultaneously Mouth bottle tumbling mill (derives from Borrow Abbe company limited Sen Weier (the Paul O. of Illinois Abbe Co.of Bensenville, Illinois)) keep 24 hours to prepare serosity.
Serosity is dried 3 hours in an oven at 100 DEG C, the most in a furnace under 1100 ° Calcine 10 hours to obtain CCT powder.Heating and cooldown rate are 10 DEG C/min Steady state value.Sieving and casing is smaller in size than the CCT powder of the gained of 50 microns, then uses and grinds Alms bowl and pestle are to obtain final powder.The stoichiometry of gained CCT powder is penetrated by X The method of ray diffraction diagram case (XRD) confirms.
The CCT powder of above-mentioned preparation is mixed with EPON 1001F and EPON 1050 epoxy solution Close and use that (EPON 1001 F: EPON 1050 weight ratio is total epoxy of 4: 1,50 weight % Resin is as in the methyl ethyl ketone of solvent and methyl iso-butyl ketone (MIBK) (1: 3 weight ratio)) and will CAF as sclerosing agent to prepare the CCT-epoxy resin solution of 30 volume %.Then by this 30 The part coating of the CCT-epoxy resin solution masterbatch of volume % is to (thickness on the Copper Foil of standard =35 microns, the ultra-thin copper material of Shu Lunke being purchased from Germany's Ross manufactures limited company (Schlenk Metallfolien GmbH of Roth, Germany) has then obtained on Copper Foil 15 To 35 microns of thick CCT-epoxy resin composition coatings.By the Copper Foil of a pair band coating with CCT-resin compound coating in the roller laminator of standard at 150 DEG C lamination facing each other. By keep at laminate in an oven 190 DEG C 4 hours to obtain the laminates of three layers, should Laminates has 35 to 70 microns of thick CCT-epoxy resin intermediate layers.
By the compound diode of gained, (it comprises 30 volume %CCT packing ring epoxide bluk recombinations Thing) cut into less sample (size of 15cm × 10cm) and their current-voltage (I- V) and conductive characteristic use Keithley 619 programmable electrometer (be furnished with Keithley 247 High voltage source unit) determine, all these Keithleys being purchased from joslyn hi-voltage Instrument company (Keithley Instruments, Inc.of Cleveland, Ohio) measures and at room temperature makes Carrying out with stepped voltage oblique ascension, wherein electric current is measured at the end of each voltage step, and record In figure 3.Under low impressed field, composite shows linear I-V characteristic (that is, electricity Stream is along with the change linear change of voltage).Along with the increase of impressed field, electric current is with nonlinear Mode promptly changes, and causes current value to change with a number of level.
Example 2
The ZnO fine powder of doping mixes with EPON 1001F and EPON 1050 epoxy resin solution (EPON 1001F: EPON 1050 with 4: 1 weight ratio, the total epoxy of 50 weight % exists As in the methyl ethyl ketone of solvent and methyl iso-butyl ketone (MIBK) (1: 3 weight ratio)) and CAF make For sclerosing agent to prepare the ZnO-epoxy resin solution of 27 volume %.Then by this 27 volume % ZnO-epoxy resin solution masterbatch the coating of a part of liquid on the Copper Foil of standard (thickness= 35 microns, the ultra-thin copper material of Shu Lunke being purchased from Germany's Ross manufactures limited company (Schlenk Metallfolien GmbH of Roth, Germany) and in an oven with 100 DEG C of dry holdings 15 Minute.By the Copper Foil of a pair band coating and ZnO-resin compound coating at the roller laminator of standard In at 150 DEG C lamination facing each other.By laminate, solidification 4 with 190 DEG C is little in an oven Time to obtain the three-layered lamination thing that gross thickness is 450 microns.The thickness in ZnO-epoxy resin intermediate layer Degree is 380 microns.
By the nonlinear diode of gained, (its ZnO filler epoxy matrix comprising 27 volume % is multiple Compound) cut into less sample (1.25 inches × 1.25 inches (3.18cm × 3.18cm)), Their current-voltage (I-V) and conductive characteristic use the electrometer of Keithley 619 programmable (being furnished with Keithley 247 high voltage source unit) measures, and all these is purchased from Keithley instrument Device company.Measure and at room temperature carry out, and result record is in the diagram.Outer power up low After the match, composite shows linear I-V characteristic (that is, electric current is along with the change of voltage and line Property ground change).Along with the increase of impressed field, electric current the most promptly changes.
Except as otherwise noted, any example the most given herein is considered as nonrestrictive. Without departing from the scope and spirit of the invention under conditions, those skilled in the art can be to this Bright carry out various amendment and change, and it is to be understood that the present invention should not be limited to this undeservedly Exemplary embodiment described in literary composition.

Claims (11)

1. a compound diode, described compound diode includes:
First conductive foil,
Second conductive foil,
It is sandwiched in the non-linear polymer between the first conductive foil and the second conductive foil multiple Condensation material layer, wherein non-linear polymer composite layer and the first and second conductive thin The length and width of sheet is substantially coextensive, and wherein non-linear polymer is combined Material is included in the non-linear inorganic particle that maintain in polymeric adhesive material, its Described in non-linear inorganic particle comprise the calcium copper titanate granule of calcining.
Compound diode the most according to claim 1, wherein said non-linear polymer is combined Material comprises the epoxy resin solidified at least in part.
Compound diode the most according to claim 1, wherein said first conductive foil and institute State the second conductive foil and comprise metal forming.
4. an electronic device, described electronic device includes according to any one of claims 1 to 3 Described compound diode.
5. an electronic device, described electronic device include embedding in the printed circuit boards compound two Pole manage, wherein said compound diode include the first conductive foil,
Second conductive foil,
It is sandwiched in the non-linear polymer between the first conductive foil and the second conductive foil multiple Condensation material layer, and wherein this non-linear polymer composite be included in polymer glue The non-linear inorganic particle that maintain in mixture material, wherein said non-linear inorganic particulate Grain comprises the calcium copper titanate granule of calcining.
Electronic device the most according to claim 5, wherein said non-linear polymer composite wood Material includes the epoxy resin solidified at least in part.
Electronic device the most according to claim 5, wherein said first conductive foil and described Second conductive foil comprises metal forming.
8. according to the electronic device according to any one of claim 5 to 7, wherein said printing electricity Road plate constitutes mobile phone, personal digital assistant, sensor or one of computer Point.
9. the method preparing compound diode, described method includes:
Forming ground floor serosity on the first conductive member, wherein this serosity includes hardenable Adhesive precursor in non-linear inorganic particle, wherein said non-linear inorganic particle Comprise the calcium copper titanate granule of calcining；
Second conductive member is formed second layer serosity；
Engaging this ground floor serosity and second layer serosity, wherein this serosity is sandwiched in first and leads Between electric components and the second conductive member；And
Harden this hardenable adhesive precursor at least in part.
Method the most according to claim 9, wherein said hardenable adhesive precursor includes Epoxy resin.
11. according to the method described in claim 9 or 10, wherein said first conductive foil and institute State the second conductive foil and comprise metal forming.
CN201180058678.XA 2010-12-06 2011-12-05 Composite diode, electronic device and preparation method thereof Expired - Fee Related CN103250473B (en)

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US9972798B2 (en) 2018-05-15
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